Organic sulfonates and methods of making and using



Patented May 2, 1950 ORGANIC SULFONATES AND METHODS OF MAKING AND USING Everett E. Gilbert. New York, and Julian A. om, Long Island City, N. Y., assignors to Allied Chemical tr-Dye Corporation, a corporation of New York No Drawing. Application January 17, 1947,

Serial No. 722,764

24 Claims. (Cl. 260-505) This invention relates to new compositions of matter and particularly to novel organic sulfonates having valuable surface-active properties and useful as detergents, wetting agents, frothing agents, dispersing agents and softening agents and as intermediates for the production of other valuable chemicals.

In the past ithas been proposed to preparetanning agents by condensation of acetaldehyde disulfonic acid withpolynuclear aromatic hydrocarbons such as naphthalene. Such products do not possess surface-active properties necessary for use as detergents, emulsifying agents and the like. Condensation products of phenols and cresols with acetaldehyde disulfonic acid also have been proposed for useas tanning agents. Preparation of surface-active products by condensation of acetaldehyde disulfonic acid with .long chain unsaturated aliphatic compounds has been suggested. Presumably in this case the acetaldehyde disulionic acid condenses with the olefinic compound by way of one of the sulfonic acid groups forming a sulfonic acid ester monosulfonate.

It is an object of the present invention to provide organic products suitable as surface-active agents for a variety of purposes. It is a further object of the invention to provide such agents by a relatively low cost procedure from inexpensive initial materials. A still further object is the production of sulfonate detergents from alkyl aromatic hydrocarbons. Further objects will be apparent from the following general description of the invention and illustrative examples thereof.

In accordance with the present invention sulfonate products having valuable surface-active properties are prepared by condensing acetaldehyde disulfonic acid with an alkyl benzene. The alkyl benzene should have at least one aromatic hydrogen atom. The condensation is effected readily at ordinary temperatures, e. g. between 5 and 40 C.

It is preferred to employ alkyl benzenes containing at least one alkyl group of two to fourteen carbon atoms, and particularly alkyl benzenes containing a single alkyl group having bebetween 3 and 8 carbon atoms in the form of a straight chain, which may contain branches to provide a total of up to 14 carbon atoms in the alkyl group. It should be understood that condensation products obtained from alkyl benzenes containing more or less carbon atoms in the alkyl group or more than one alkyl group also possess valuable surface-active properties. have found that the compounds of the group' defined by the specified limitations are particularly valuable in this respect.

The compounds of the invention not only are valuable in the form of free acids or metal salts as detergents, lubricants, softening agents, and

However, we 4 the like but also are suitable for manufacture of other chemicals by conversion of the sulfonate group in known manner. Thus, sulfonyl chlorides, sulfonyl fluorides and other derivatives may be prepared. For use as detergents, emulsifiers, wetting agents, foaming agents, surface tension depressants and the like it is desirable to employ the sulfonates of the invention in the form of salts having water-soluble-soap-forming cations, such as the sodium, potassium, and ammonium salts, and the salts of amines, e. g. ethyl and methyl amine, ethanol-amine, diethanolamine, triethanol-amine, pyridine, aniline, and ethylene diamine, i. e. salts of metals, amines, and the like which form water-soluble salts of stearic acid and otherhigher fatty acids commonly used in soap making. The normal salts have a pH in dilute aqueous solution very close to 7. However, the detergent compositions are effective in acid solutions as well as in neutral and alkaline solutions. In acid solutions it is probable that a part of the composition is present as the free acid. The condensation products of the invention may contain one or two sulfonate groups in the molecule and many of the products comprise mixtures of monoand disulfonates. Thus, some of'the products in acid solution may form the acid salt, whereas others form merely a mixture of the free acid and the normal salt. It is noted in this connection that analytical data for alkali metal and sulfur contents have indicated some of the most valuable surface-active agents of the invention to comprise merely the monosulfonate. This is the case with secondary butyl benzene and amyl benzene condensation products.

Surface-active agents within the purview of the invention have been obtained by condensation of acetaldehyde disulfonic acid with toluene, xylenes or xylene mixtures, ethyl benzene, isopropyl benzene, polyethyl benzenes (such as the higher boiling by-products of the production of ethyl benzene, containing mostly diand tri-ethyl benzene), tertiary butyl benzene, secondary butyl benzene, secondary amyl benzene, and mixed mono-alkyl benzenes with average carbon contents of 5, 8 and 13 carbon atoms, respectively, in the alkyl groups and comprising for the most part primary and secondary alkyl benzenes in which the alkyl groups comprise straight and branched chain isomers of the designated numbers of carbon atoms, obtained by condensation of benzene with mixtures of isomeric oleflns.

The condensation process may be carried out using catalysts or dehydrating agents eifective for promoting condensations of the type involving removal of aldehyde oxygen and aromatic hydrogens to form the diaryl, or in this case, the dialkaryl methane nucleus. Examples of such agents are sulfuric acid, phosphoric acid, phosphorus pentoxide, hydrogen fluoride, boron trifluoride.

The sulfonate condensation products of the invention are preferably made by adding the alkyl benzene gradually to a solution of the acetaldehyde disulfonic acid or an alkali metal salt thereof in concentrated sulfuric acid at a temperature between 5 and 40 C. until a slight excess, for instance about 2.2 mols of the alkyl benzene per mol of the acetaldehyde disulfonate has been added. In the case of the condensation products derived from alkyl benzenes containing two or more carbon atoms per alkyl group, the product may be separated from excess sulfuric acid by dilution with water. This dilution causes separation of the condensation product as an oil, lighter than the sulfuric acid liquor, and this condensation product may be converted to a salt having a water-soluble soap-forming cation and organic sulfonic acid anion by conventional saltforming procedures; for instance, it may be converted to an alkali metal salt by treatment with an alkali such as sodium hydroxide, potassium hydroxide, ammonia, sodium carbonate, etc. For purposes in which the presence of inorganic salt is not objectionable, the entire mixture may be neutralized to provide a mixture of the alkali metal" sulfonate and alkali metal sulfate. This procedure is of especial utility in the production of alkali metal salts of condensation products of toluene and xylene which do not separate from acid as separate phases upon dilution with water.

The following examples further illustrate the invention and particularly the preparation and valuable properties of the products thereof. In the examples quantities are expressed in terms of weight unless otherwise indicated.

Example 1.-About 300 parts of potassium acetaldehyde disulfonate monohydrate (1.0 mol) was mixed with 900 parts of 95-96% H2504 and the mixture was cooled to 5 C. 325 parts of secondary amyl benzene (2.2 mols) was added at an approximately constant rate in a period of 20 minutes while th reaction mixture was agitated vigorously. After all of the amy1 benzene was added, the mixture was agitated for an additional three hours at 5-7 C. Stirring was then continued for an additional 2 /2 hours while the temperature was allowed to rise gradually to 30-35 C. The mixture was then poured into 2000 parts of water at C. The resulting oil layer was separated from the water by decantation and was neutralized to a pH of about 7 by the addition of 210 parts of 18% NaOH solution. The neutralized .mixture was dried at a temperature of about 100 C. and ground to a powder. 370 parts of a light yellow product was obtained, which yielded the following surface tension and Draves test results.

Concentration Surface Tension in Distilled at 0. 32?. 6 Water (dynes per cm.)

Per Cent Seconds 0. 30 31 4 0. 20 29 6 0. 10 34 14 0. 34 36 0. 01 42 Example 2.-The process of Example 1 was repcated substituting 2.2 mols of ethylbenzene for the 2.2 mols of amyl benzene used in that exampie. The oil-likeproduct separated upon dilutim was neutralized by adding 1.7 mols of potas- 4 sium hydroxide as an 18% aqueous solution and the product was dried at about C. and ground. The product yielded a 0.30% aqueous solution giving a surface tension measurement at 30 C. of 38 dynes per cm.

Example 3.The process of Example 1 was repeated employing 2.2 mols of secondary butyl benzene in place of the secondary amyl benzene. The product yielded an aqueous 0.30% solution which at 30 C. had a surface tension of 33 dynes per cm. The potassium salt prepared in a similar manner yielded a 0.30% solution which at 30 had a surface tension of 34 dynes per cm. The potassium salt also yielded the following data when tested at 25.5 C.

Concentration Surface 'lenin Distilled slon at 25.5 0.

Water (dynes per cm Per Cent Example 4.-The process of Example 1 was repeated substituting an amyl benzene mixture containing isomeric amyl benzenes obtained by condensation of benzene with a commercial amylene mixture of petroleum origin for the secondary am'yl benzene in Example 1. The grczguct yielded the following surface activity Concentration Surface Tenin Distilled sion at 28 0. igg '6 Water (dynes per cm.) a

Per Cent Seconds 0. 30 31 3 0. 20 25 5 0. 10 32 20 0. 0 33 48 U. 01 41 J Concentration Surface Tenin Distilled sion at 21 0. giggi, 'g

Water (dynes per cm.)

Percent Seconds 30 31 Example 6.2.'7 parts of acetylene was slowly introduced into a mixture of 33 parts of liquid S03 and 210 parts of liquid S02 at 20 to 30" C. To the resulting mixture 71 parts of 80% H2804 solution was added gradually while S0: was permitted to evaporate. After all of the sulfuric acid was added, the mixture was stirred for 15 minutes and 33 parts of secondary amyl benzene was added gradually while the mixture was agitated. The addition required about 10 minutes. The mixture was then agitated at l0 to +10 C. for three hours and then was stirred for an additional 1 hours without cooling. The

resulting mixture at a temperature of about 35 C. was poured into 200 parts of water and the resultant oil layer was separated and neutralized as described in Example 1. The surface tension Surface Ten- Condensation Product oi sion (dyncs per cm.)

15th! benzene 38 Tar at I benzene 42 (lu-aiky benzene (branched chain mixed alkyl) 44 We claim:

l. A new composition of matter comprising an organic sulfonate obtained in the form of the free acid by reaction of acetaldehyde disulfonic acid with twice its molecular ratio of an alkyl benzene in the presence of an aldehyde con densation type of condensing agent.

2. A new composition of matter comprising an organic sulfonate obtained in the form of the free acid by reaction of acetaldehyde disulfonic acid with twice its molecular ratio of alkyl benzene having an alkyl group with between 2 and 14 carbon atoms in the presence of an aldehyde condensation type of condensing agent.

3. A surface-active organic sulfonate having a water-soluble soap-forming cation and an organic sulfonic acid anion obtained in the form of the free acid by reaction of acetaldehyde disulfonic acid with twice its molecular ratio of alkyl benzene having an alkyl group with between 2 and 14 carbon atoms in the presence of an aldehyde condensation type of condensing agent.

4. A surface-active organic alkali metal sulfonate obtained in the form of the free acid by reaction of acetaldehyde disulfonic acid with twice its molecular ratio of alkyl benzene having an alkyl group with between 2 and 14 carbon atoms in the presence of an aldehyde condensation type 01' condensing agent.

5. A surface-active organic alkali metal sulfonate obtained in the form of the free acid by reaction of acetaldehyde disulfonic acid and an alkyl benzene having an alkyl group containing between 3 and 14 carbon atoms, between 3 and 8 of which are arranged as a straight chain, as its sole nuclear substituent in the presence of an aldehyde condensation type of condensing agent.

6. A surface-active organic alkali metal sulfonate obtained in the form of the free acid by reaction of acetaldehyde disulfonic acid with twice its molecular ratio of alkyl benzene having an alkyl group containing between 3 and 14 carbon atoms, between 3 and 8 of which are arranged as a straight chain, as its sole nuclear substituent in the presence of an aldehyde condensation type of condensing agent.

7. A surface-active organic sulfonate having a water-soluble soap-forming cation and an organic sulfonic acid anion obtained in the form of the free acid by reaction of acetaldehyde disulfonic acid with twice its molecular ratio of amyl benzene efl'ected with a sulfuric acid condensing agent.

' 8. A surface-active organic alkali metal sulfonate obtained in the form of the free acid by reaction of acetaldehyde disulfonic acid with twice its molecular ratio of amyl benzene eiiected with a sulfuric acid condensing agent.

9. A surface-active organic alkali metal sulfonate obtained in the form of the free acid by reaction of acetaldehyde disulfonic acid with twice its molecular ratio of a branched chain octyl benzene efl'ected with a sulfuric acid condensing agent.

10. A surface-active organic sodium sulfonate obtained in the form of the free acid by reaction of acetaldehyde disulfonic acid and an alkyl benzene having an alkyl group containing between 3 and 14 carbon atoms, between 3 and 8 of which are arranged as a straight chain in the presence of an aldehyde condensation type of condensing agent.

11. A surface-active organic sodium sulfonate obtained in the form of the free acid by reaction of acetaldehyde disulfonic acid with twice its molecular ratio of secondary amyl benzene efiected with a sulfuric acid condensing agent.

12. A surface-active organic sodium sulfonate obtained in the form of the free acid by reaction of acetaldehyde disulfonic acid with twice its molecular ratio of di-isobutyl benzene effected with a sulfuric acid condensing agent.

13. The method of making an organic sulfonate, which comprises condensing acetaldehyde disulfonic acid with twice its molecular ratio of alkyl benzene in the presence of a condensing agent of the type promoting removal of aldehyde oxygen and aromatic hydrogen atoms.

14. The method of making an organic sulfonate. which comprises condensing acetaldehyde disulfonic acid with twice its molecular ratio of an alkyl benzene having'an alkyl group with between 2 and 14 carbon atoms by means of a sulfuric acid condensing agent.

15. The method of making a surface-active organic alkali metal sulfonate, which comprises condensing acetaldehyde disulfonic acid with twice its molecular ratio of an alkyl benzene having an alkyl group with between 2 and 14 carbon atoms, in the presence of a condensing agent of the type promoting removal of aldehyde oxygen and aromatic hydrogen atoms, and neutralizing the resulting organic sulfonic acid with an alkali metal compound.

16. The method of making a surface-active organic sulfonate, which comprises condensing acetaldehyde disulfonic acid and a monoalkyl benzene having an alkyl group containing between 3 and 14 carbon atoms, between 3 and 8 of which are arranged as a straight chain, by means of a sulfuric acid condensing agent, and neutralizing the resulting organic sulfonate with an alkali metal compound.

17. The method of making a surface-active organic sulfonate, which comprises condensing acetaldehyde disulfonic acid with twice its molecular ratio of alkyl benzene having a single alkyl group containing between 3 and 14 carbon atoms, between 3 and 8 of which are arranged as a straight chain, by means of a sulfuric acid condensing agent, and neutralizing the resulting organic sulfonate with an alkali metal compound.

18. The method of making a surface-active organic sulfonate, which comprises condensing acetaldehyde disulfonic acid with twice its molecular ratio of secondary amyl benzene by means of a sulfuric acid condensing agent and neutraltctive sulfonate as defined in claim 3.

2l."I"he method of improving the surface activity 01 water, which comprises incorporating therein between 0.01% and 0.3% of a surfaceactive 'sulfonate as defined in claim 4.

The method of improving the surface ac- 22. tivity of water, which comprises incorporating therein between 0.01% and 0.3% of a surface- 20 active'sulfonate as defined in claim 6.

23, The method of improving the surface activity 0! water, which comprises incorporating therein between 0.01% and 0.3% of a surfaceactive sulionate as defined irr'claim 11.

24. The method of improving the surface activity of waste which comprises incorporating therein between 0.01% and 0.3% oi a surfaceactive sulionate as defined in claim 12.

EVERE'I'I E. GILBERT. JULIAN A. O'I'IO.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,232,620 Stiasny July 10, 1917 1,237,405 Stiasny Aug. 21, 1917 2,029,073 Huttenlocher et a1. Jan. 28, 1936 2,126,232 Voss et al Aug. 9, 1938 2,218,996 Vosset a1 Oct. 22, 1940 OTHER REFERENCES Bayer, Ben. v. '1, (1874) p. 1190, 1 p.

Staudinger et 9.1., Ben, v. 49. (1916) pp. 1950- 1951, 2 pp.

Kharasch et a1., J.A.C.S., v. 61, (1939) p. 3092, 

1. A NEW COMPOSITION OF MATTER COMPRISING AN ORGANIC SULFONATE OBTAINED IN THE FORM OF THE FREE ACID BY REACTION OF ACETALDEHYDE DISULFONIC ACID WITH TWICE ITS MOLECULAR RATIO OF AN ALKYL BENZENE IN THE PRESENCE OF AN ALDEHYDE CONDENSATION TYPE OF CONDENSING AGENT. 